Process for dyeing or printing cellu-



United States Patent PROCESS FOR DYEING 0R PRINTING CELLU-LOSE-CONTAINING MATERIALS AND CQMPO- SITIONS SUITABLE THEREFOR JacquesWegmann and Karl Menzi, Basel, Switzerland, assignors to Ciba Limited,Basel, Switzerland, a Swiss firm No Drawing. Application November 25,1952, Serial No. 322,548

Claims priority, application Switzerland December '7, 1951 13 Claims.(Cl. 8-42) This invention provides a valuable process for dyeing orprinting cellulose-containing materials, in which a neutral to alkalinedyebath or printing paste is used which contains a direct dyestuft inwhich a metal having an atomic number from 27 to 29 is bound in complexunion to at least one ortho-hydroxy-ortho'-carb0xy-azo-grouping, analiphatic a-amino-carboxylic acid, and phosphorus containing anions of aphosphoric acid of the constitution Hm+2PmO3m+1 in which in represents awhole number greater than 1.

The dyebath may be prepared either directly in the concentrationnecessary for dyeing or advantageously by diluting a so-called stocksolution which is of the above composition but contains the ingredientsin a concentration too high for direct use. For printing pastessolutions having a high concentration of dyestufi are always necessary.

The dyestulfs used in the process of the invention are direct dyestuffswhich contain a metal having an atomic number from 27 to 29, that is tosay, cobalt or especially nickel or copper, and above all copper, boundin complex union to at least oneortho-hydroxy-ortho'-carboxyazo-grouping. As direct dyestuifs there areto be understood only those which possess a suiiiciently good solubilityin water to enable them to be used in concentrations usual in dyebathswithout the addition of agents enhancing solubility. This is the casewhen the solubility of the dyestufr" is such that at least about gramsof the dyestufi dissolve in one liter of hot water.

The dyestuffs contain at least one of the above mentioned metals boundin complex union to an orthohydroxy-ortho'-carboxy-azo-grouping. Amongthese complex atomic groupings are those represented by the formulae inwhich Me represents the metal atom bound in complex union, namely Co, Nior Cu. The formulae undoubtedly give the correct stoichiometric quantityof metal and the correct position of the metal atom in the complex, butthe distribution of main and secondary valencies in the complex union ofthe metal wtih the dyestufi has not up to now been established withcertainty.

There come into consideration principally dyestuffs having two azolinkages. The azo linkages of a single dyestufl may be present wholly orpartially in the form of metallizedortho-hydroxy-ortho-carboxy-azo-groupings. Furthermore, the dyestufismay also contain other groupings capable of forming metal complexes, forexample, ortho:ortho-dihydroxy-azo-groupings or salicyl groups,advantageously the former are also present in the form of heavy metalcomplexes and the latter not in the form of metal complexes.

It is also of advantage that any ionogenic acid groups "ice in thedyest'uifs, that is to say, especially sulfonic acid or carboxylic acidgroups (insofar as the latter are not present in the form ofortho-hydroxy-ortho'-carboxy-azometal complexes), should be present inthe form of alkali metal salts.

As aliphatic a-amino-carboxylic acids there are advantageously used theeasily accessible acids of simple constitution such, for example, asoc-ElliliIlO-PI'OPlODiC acid (alanine), methylamino acetic acid(sarcosine), flhydroxyethylarninoacetic acid and especially aminoaceticacid (glycocoll).

In addition to the dyestuii of the e-aminocarboxylic acid the dyebathscontain phosphorus-containing anions of a phosphoric acid of theconstitution in which m represents a whole number greater than 1. Therecome into consideration, for example alkali salts of the polyphosphoricacids of the formulae HsP4013 and HsPaOm, and especially those ofpyrophosphoric acid (HaPzO't).

With regard to the relative proportions of the above describedingredients which are present in the solutions or printing pastes or areused for making them, the following observations should be noted:Advantageously the proportion of the u-amino-carboxylic acid shouldamount to about one-tenth to one-half of the quantity of dyestuff assuch, that is to say, excluding any substantial quantities of salts suchas sodium sulfate or other diluents. in some cases larger quantities ofthe a-amino-carboxylic acids may have a disadvantageous effect. Thequantity of phosphate ion advantageously amounts to one-fifth to doublethe quantity of the dyestutf. Good results are obtained in most caseswith about equal quantities of dyestufi? and a crystallinetetra-alkali-pyrophosphate, but in general larger quantities ofphosphorus-containing anions have no disadvantageous efiect.

The order of succession in which the necessary ingredients are added tothe water for preparing the stock solutions and dyebaths is entirelyoptional andusually has no influence on the result. However, goodresults are frequently impaired if, in preparing solutions of highconcentration, there are added in addition to the aforesaid substancesappreciable amounts of other electrolytes, so that it is of advantage toavoid such additions. For this reason it is generally desirable to usethe metalliferous dyestufis, not in a form made up to a certain strengthby means of sodium sulfate or sodium chloride, but in the form in whichthey are customarily isolated during their manufacture, and in whichthey do not contain disadvantageous quantities of those salts.

The disadvantageous effect of electrolytes consists mainly in impairingthe process of dissolution which, although it is hardly noticeable inhigh dilutions, for example, at the concentrations ordinarily used indyebaths, at high concentrations, such as are necessary in stocksolutions, printing pastes and in some cases in machine dyeing, can leadto incomplete dissolution of the dyestuif.

The dyebaths and printing pastes used in the process of the inventionmust have a neutral or advantageously alkaline reaction. When thereaction is not already alkaline, for example, due to the presence oftetra-sodium pyrophosphate, an alkaline reaction can be produced by theaddition of suitable substances of alkaline reaction, such as an alkalihydroxide, trisodium ortho-phosphate, ammonia or ethanolamine. However,for the reasonsexplained above it is in some cases disadvantageous touse for this purpose an alkali carbonate or bicarbonate.

Instead of preparing the dyebaths, stock solutions or printing pastes bydissolving the necessary ingredients separately and in succession inwater, it is in general of advantage to make up the aforesaidingredients in the form of dry preparations.

Valuable preparations are, for example, those which contain a directdystufi of the kind hereinbefore defined and an aliphatica-amino-carboxylic acid or an alkali phosphate as defined above. Suchpreparations can be used for preparing stock solutions, dyebaths andprinting pastes, the lacking compound which contains thephosphorus-containing anions or the lacking a-arninocarboxylic acidbeing added to the solution.

However, it is usually of advantage to make up preparations whichcontain, in addition to the direct dyestuff, the aliphatica-amino-carboxylic acid and also the phosphoruscontaining anions, forexample in the form of the anion of an alkali salt of the phosphoricacid in question.

When the preparations are to be made up to a predetermined strength itis of advantage to choose for this purpose, for example, a larger orsmaller quantity of the alkali pyrophosphate or polyphosphate or to adda nonelectrolyte such as urea or a water-soluble carbohydrate such assaccharose or dextrin. As stated above, the usual diluents such assodium sulfate often have a disadvantageous effect. In the case of someof the aforesaid dyestufis the disadvantageous effect of such additionsconsists in considerably reducing the favourable action of thea-aminocarboxylic acid of the phosphorus compound.

In other respects dyeing with the solutions used in the presentinvention is carried out in a manner in itself known for direct-dyeingdyestuffs. Similarly, printing pastes are advantageously made up in theusual manner with thickening agents known to be suitable for use withdirect dyestuffs and are used in known manner.

In the case of those dyestuffs defined above which are sutficientlysoluble for preparing stock solutions of the usual concentration and fordyeing from dilute baths, but have too little solubility for thepreparation of stock solutions of higher concentration, such as arenecessary for printing pastes and for machine dyeing, the presentinvention makes it possible to increase the solubility to such an extentthat the dyestuffs can generally be used without difficulty for theselatter purposes. Furthermore, in some cases it is possible in accordancewith the present process to produce stronger and purer tints. Inaddition to this the a-aminocarboxylic acids together with thephosphates enable some dyestuffs to penetrate more rapidly and moredeeply into the cellulose fiber, and this is of advantage in variousconnections, for example, in that it enables dyeings to be producedwhich are especially uniform or especially strong and yet have nobronzing effect, and this result can be obtained within a relativelyshort time. From this it will bc-'nnderstood that the process isespecially useful for dyeing in a continuous manner, for example, indyeing on the foulard. Finally, in some cases the control of the speedof absorption of the dyestufls from the dyebaths by the fractionaladdition of salt is improved by the process of the invention as comparedwith the use of dyebaths not containing the additions characteristic ofthe invention.

In certain cases it is desirable to after-treat dyeings or printsproduced by the present process with agents which enhance theirproperties of wet fastness. As products suitable for this purpose theremay be mentioned:

the reaction products of formaldehyde with compounds such as cyanarnide,dicyandiamide, dicyandiamidine, or melamine. There also come intoconsideration aftertrcating agents which are not prepared withformaldehyde. After-treating agents combined with copper salts may heused more especially for dyeings or prints produced with dyestuffs whichcontain further free metalllzable groups.

The following examples illustrate the invention, the parts andpercentages being by weight.

Example 1 10 parts of the dyestuff of the formula are mixed with 1 partof glycocoll and 9 parts of crystallized sodium pyrophosphate. Themixture is dissolved at the boil in parts of water.

20 parts of the resulting stool; solution are added to a dyebath of 2880parts of water at 60 C. and 30 parts of crystalline sodium sulfate areadded.

lOO parts of cotton are entered into the bath and the temperature israised to 90-95 C. in the course of V: hour. The bath is maintained atthat temperature for one hour, and after rinsing and drying there isobtained a yellowish brown dyeing, which is purer and stronger than adyeing prepared with the same quantity of the dyestuff but without theaddition of glycocoll and sodium pyropnosphatc, and with a much greaterquantity of water in order to dissolve the dyestuff.

In spite of the alkaline reaction of the bath, cellulose acetate silkeffect threads remain pure white, whereas in a control bath, which isgiven the same pH value by the addition of sodium carbonate and containsneither glycocoll nor pyrophosphate, the cellulose acetate silk effectthreads are stained.

Effect threads of wool are dyed the same tint, whereas in a control baththe dyestuff absorbed on to the wool is decomposed and the wool effectthreads are colored a dirty grey.

If the above procedure is repeated, except that parts of crystallinesodium sulfate are used instead of 30 parts, the bath is practicallycompletely exhausted, and a dyeing is produced which is considerablymore powerful than the control dyeing produced without glycocoli andpyrophosphate. Completc absorption of the dyestuff cannot be broughtabout without the latter additions, as the dyestuff begins to fiocculateout when 60 or more parts of crystalline sodium sulfate are present inthe dyebath, and the precipitated dyestuff is lost to the dyeingprocess. The difference in the purity of the tint is considerablygreater in this case than in dyeing as described above with only 30parts of sodium sulfate.

By increasing the quantities of the stock solution from 20 parts to 40or 30 parts, and otherwise dyeing in the manner described above, aconsiderable increase in dyeing strength and purity over the controldyeing is also ob served. The control dyeing cannot be improved by usinga greater quantity of the salt addition, as at these higher dyestutfconcentrations the tendency of the dyestutf to flocculate out is stillmore pronounced. With the product containing glycocoll andpyrophosphate, on the other hand, the stronger dyeing produced by theincreased addition of electrolyte can be still further increased.

2,749,206 r 5 r i 6 Example 2 is raised to the boil in the course of /2hour, and dyeing l parts'of the concentrated dyestulf of the formula icarried on for one hour at that Pf There 7 is obtained an extremelystrong yellow tint having very good properties of fastness. The dyestufiitself, that is 'O' C 5 to say, without the addition of glycocoll andpyrophos- N=NG I E phate, is unsuitable for this method of dyeing,because a 8051 H it requires 1000 parts of water to dissolve thedyestuif, and the dyestulf will not tolerate any addition of sodium 0:0sulfate without fiocculating out. OH; 7 10 By using instead of thecopper complex, the nickel complex of the aforesaid dyestuif, theimprovement is soaH Hose even more marked, and still purer yellowdyeings hav- I I I I ing remarkable properties of fastness are produced.

C-N-C (JH=0H--NH coo-ou-$ Example 3 are mixed with 1.5 parts ofglycocoll and 2 parts of crys- 10 parts of the dyestufi of the formulatalline sodium pyrophosphate. The mixture is soluble are mixed with 1part of glycocoll and 9 parts of crystaL in 250 parts of boiling water,whereas without the glyco- 11116 Sodlllm PY P P The mlXtul'e 1S l ed ton 1000 a t of Wate ecessar notwithstandino 1 8 a clear solution in 100parts of water whereas 10 parts gresence 5 i gzgig y n of the dyestutfmixed with 10 parts of crystalline sodium sulfate require 10 times thequantity of water.

By dyeing in the Wanner in Example 1 100 The mixture with glycocoll andsodium pyrophosphate parts of cotton or viscose artificial silk with 3parts of yields a pure yellowish brown tint, whereas with the same themixture of dyestuif, glycocoll and sodium pyrophosdyestufi mixed onlywith sodium sulfate a duller more phate, there is obtained a clearyellow tint of extraordireddish brown tint is produced. nary fastness tolight and good fastness to water. Example4 By adding to the rinsing bath1 gram per liter of a 10 parts of the dyestuff of the formula oou--o HIg-C N so H HO s N ifii ITI l 3 3 o Cu-OOC I m- NH C HN CHHOM a r 3 N CN=NSOzNHz CH condensation product of formaldehyde and dicyandiamide aremixed with 1 part of glycocoll and 9 parts of crystalthe dyeing acquiresa very good fastness to soap/ sodium line sodium pyrophosphate, and themixture is dissolved carbonate washing. in 200 parts of boiling Water.The soiution is diluted The dyeing has the same properties of fastnessas a with water to give 800 parts and a fabric of staple fibers controldyeing produced without the addition of glycocoll of regeneratedcellulose is foularded with the resulting and phosphate, but it excelsthe control dyeing with re- S lution. The dyeing is then developed for10 minutes gard to purity of tint. in a boiling bath containing, perliter, 50 grams of sodium With this dyestuff it is easy to produce verystrong yelchloride. There is produced a strong reddish brown tint lowtints in dyeing machineswith the use of a very short Which isexcellently through-dyed. This procedure which liquor ratio, which isnot possible without the addition iS especially favorable forthrough-dyeing naps can be of glycocoll and pyrophosphate owing to thedifliculty used, Without the addition of glycocoll and PY P with regardto the solubility of the dyestufi being im- P y to P paler Finis, as acollespflnding paired. For example, 10 parts of the dyestulf mixed q f yOf [110 dyestufi made 1 With Sodium Sulfate i h l ll d di pyrophosphate(see above) requires 1000 parts of water to dissolve it at the boilingmay be dissolved in 400, parts of boiling water and the }P IfIOWeVEP, 0temperature can h r ly be solution poured into 200 parts of water in adyeing jigger. mamtamed durmg foulardmg- After the addition of 10 partsof crystalline sodium sul- Example 5 fate 200 parts of cotton areentered, the temperature 10 parts of the dyestutf of the formula l i p03H HOHS s N N 7 which contains but a little salt, are mixed with l-part27 to 29 is bound in complex union to at least one orthoof sarcosine and9 parts of crystalline sodiumpyrophoshydroxy-orhto'-carboxy-azo-group1ng, a water soluble ahphate anddissolved in 300 parts of boiling water. Withphat1c a-amino-carboxyhcacid, and an alkali metal salt out the addition of sarcosine 100 partsof water would of a phosphoric acid of the constltution be necessary. l3y replaci g the sarcosine by the same 5 Hm +ilsmoam +1 quantity ofalamne (a-ammopropionic acid) there is obmi a preparation f similar goodSolubility in which m represents a whole number greater than B d ivegetable fib with this mixture in the 2. Process for coloring textilematerials contain ng manner described in Example 1 there are producedcellulosic fibers with metalliferous direct dyestuffs, wh ch 1 dyeingshaving very good ijroperties of fastness to comprises applying to saidmaterials a neutral to alkaline light and Water, and as compared withdyeings produ d aqueous dyestuff composition which contains a directdyefrom the dyestuff mixed only with crystalline sodium Stuff Whlch afnetal havmg P atom: number from 27 lf t they possess greater purity to29 is bound in complex union to at least one ortho By after-treatment inthe rinsing bath for 10 minutes P Y- F Y-? s P e a watcf'solublc i h 2grams per liter f a product consisting of 25 parts phatic warninocarboxylic acid, and an alkali metal pyroof copper acetate and 75 partsof a condensation product phosphate" of 1 mol of dicyandiamide and 2.2mols of formaldehyde, Process colonng Fextlle miftenals contammg P thereis obtained a more greenish dyeing which iS con lulosic fibers withmetaihferous direct dyestuffs, wh ch siderably improved with respect toits fastness to washing. comprises applymg to y! matelilals 3 q 9alkalmc By using in the above mixture, instead of tetra-sodium aquequsdyestuff composition which contains a direct dye pyrophosphate, the samequantity of hexasodium tetra- Stuff whlch *i atomlc number frompolyphosphate a simih1r good result is obtained to 29 1S bound lIlcomplex union to at least one ortho-hydroxy-ortho-carboxy-azo-group1ng,ammoacetic acid, and Example 6 an alkali metal pyrophosphate.

15 parts of the dyeshiii mentioned iI1 Example 3 are 4. Process forcoloring textile materials containing mixed with 2 parts of giycocoii 13parts f crystalline cellulosic fibers with metalliferous directdyestuffs, WhlCll tetrasodiurn pyrophosphate and 150 parts of urea, andthe comprises pp y to g materials a nehtral Q a ka ln mixture isdissolved in 395 parts of Water at the boil. aquehus dlfeshlffcomPoslhoh f cohtalhsh dll'ect y The resulting solution is poured whilestirring into 500 Stuff 111 Whlch PP 1s holuhd 1h cOITIPREX UIIIQH to$1985! parts of neutral tragacanth thickening, which contains 30 30 h yy' h Y- -g p g, ammoparts of dry substance, and 5 parts of sodiummetanitroacetic acid, and all alkhh metal PY P Q P benzene sulfonate aredd d 5. Process for coloring textile materials containing cel- A cottonfabric a fabric of Staple fibers of regenerated lulosic fibers withmetailiferous direct dyestuffs, which cellulose and a fabric of viscoseartificial silk are printed Comprises applying to i matehlals a falkaline with the resulting printing colon aqueous dyestufi compositionWhlCll contains a dlrect dye- Th prints are d i d d h Steamed f minutesstuff in WhlCl'l a rnetal having an atomic number from 27 They are thenthoroughly rinsed in cold water and dried. to 29 is bound complex unlonto at lifast 9- On all three fabrics there are obtained yellowish brownhydmxlf'or [110"Carboxy'azo'groupm amlhoacchc acld, level prints of verygood fastness to light and washing. and Sodmm Pymphospham By adding tothe rinsing bath 3 grams per liter of a prod- 4 6. Process for coloringtextile materials containing c eluct, consisting of 20 parts of sodiumcopper tartrate and 11110516 fibers With mfitalhfel'ous (11mt dyestuffs,which 80 parts of a condensation product of dicyandiamide andCOITIPI'I'WS pp y to said materials a neutral to alkaline formaldehyde,and dissolved with one half its weight of aqueous dyesuttf compositionwhich contains the dyeammonia solution, and carrying on the treatmentfor 10 stulf of the formula COO--Cu-O 11H N N coon N N we Nat aNH MGOHminutes, the prints are also given a good fastness to washaminoaceticacid, and sodium pyrophosphate. ing. 7. Process for coloring textilematerials containing cel Example 7 lulosic fibers with metalliferousdirect dyestuffs, which 20 parts of the dyestulf mentioned in Example 2are comprises applying to said. {naterials a to alkaline mixed with 4parts of glycocoll and 8 parts of crystalline aquous dyesmfi composmonwhlch comams the tetra-sodium pyrophosphate. 150 parts of urea areadded, stufi of the formula and the whole is dissolved in 295 parts ofboiling water. The resulting solution is stirred into 500 parts of neu Ic =c NH tral tragacanth thickening (containing 30 parts of dry O isubstance), and a further 20 parts of crystalline tetra-sono diumpyrophosphate and 5 parts of sodium meta-nitrobenzene sulfonate areadded. 4

A viscose fabric is printed, dried and steamed for 10 OH minutes,whereby a good level yelow print is obtained. What we claim is:

1. Process for coloring textile materials containing cel- Q EN-C/ I I llulosic fibers with metalliferous direct dyestuffs, which O comprisesapplying to said materials a neutral to alkaline i (LN aqueous dyestuffcomposition which contains a direct COO C11 "O dyestuff in which a metalhaving an atomic number from aminoacetic acid, and sodium pyrophosphate.

stuff of the formula aminoacetic acid, and sodium pyrophosphate.

9. Process for coloring textile materials containing cellulosic fiberswith metalliferous direct dyestuffs, which comprises applying to saidmaterials a neutral to alkaline 10 12. A dyestuff preparation suitablefor being applied on textile materials containing cellulosic fibers,which contains a direct dyestufi in which a metal having an atomicnumber from 27 to 29 is bound in complex union to at 5 least oneortho-hydroxy-ortho'-carboxy-azo-grouping, an

aliphatic a-amino-carboxylic acid, and an alkali metal salt of aphosphoric acid of the constitution aqueous dyestulf composition whichcontains the dye- 20 in Which represents a Whole number gTeatel' thanstuff of the formula N O nossmmrii N S OzNHa aminoacetic acid, andsodium pyrophosphate.

10. Process for coloring textile materials containing cellulosic fiberswith metallit'erous direct dyestuffs, which comprises applying to saidmaterials a neutral to alkaline aqueous dyestuif composition whichcontains the dyestuflf of the formula 13. A dyestuif preparationsuitable for being applied on textile materials containing cellulosicfibers, which contains a direct dyestuff in which copper is bound incomplex union to at least one ortho-hydroxy-ortho'-carboXy-azogrouping,aminoacetic acid, and sodium pyrophosphate.

in which m represents a whole number greater than 1.

References Cited in the file of this patent FOREIGN PATENTS France Feb.12, 1934 OTHER REFERENCES Chemical Technology of Dyeing and Printing byL. Diserens, translated by Wengraf and Baumann, New York city, 1948,Reinhold Publishing Corp., pgs. 8 to 19.

Journal Soc. Dyers and Colorists for June 1949, pg. 313.

1. PROCESS FOR COLORING TEXTILE MATERIALS CONTAINING CELLULOSIC FIBERSWITH METALLIFEROUS DIRECT DYESTUFFS, WHICH COMPRISES APPLYING TO SAIDMATERIALS A NEUTRAL TO ALKALINE AQUEOUS DYESTUFF COMPOSITION WHICHCONTAINS A DIRECT DYESTUFF IN WHICH A METAL HAVING AN ATOMIC NUMBER FROM27 TO 29 IS BOUND IN COMPLEX UNION TO AT LEAST ONE ORTHOHYDROXY-ORTHO''-CARBOXY-AZO-GROUPING, A WATER-SOLUBLE ALIPHATIC A-AMINO-CARBOXYLICACID, AND AN ALKALI METAL SALT OF A PHOSPHORIC ACID OF THE CONSTITUTION